CN1049218C - Ｒ－四氢噻唑－２－硫酮－４－羧酸的合成方法 - Google Patents

Ｒ－四氢噻唑－２－硫酮－４－羧酸的合成方法 Download PDF

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CN1049218C
CN1049218C CN95100935A CN95100935A CN1049218C CN 1049218 C CN1049218 C CN 1049218C CN 95100935 A CN95100935 A CN 95100935A CN 95100935 A CN95100935 A CN 95100935A CN 1049218 C CN1049218 C CN 1049218C
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carboxylic acid
synthetic method
thione
present
ttca
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CN1125228A (zh
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李叶芝
胡学山
黄化民
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Jilin University
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Jilin University
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明属于R-四氢噻唑-2-硫酮-4-羧酸(简称(R)TTCA)的合成技术。
本发明是采用L-半胱氨酸，二硫化碳在NaOH及无机盐存在下，合成(R)TTCA，其特点是原料易得，成本低，合成方法简单，产率高，可达85-92%。

Description

本发明属于R-四氢噻唑-2-硫酮-4-羧酸的合成技术。
R-四氢噻唑-2-2-硫酮-4-羧酸(简称(R)TTCA)，分子中含有羧酸基和硫酰胺基两个功能基团，具有很好的化学选择性及手性识别功能。可作为手性源和拆分试剂，也可用来做镇痛剂、植物生长抑制剂、测定尿样中CS2含量的标准样等，因此(R)TTCA化合物引起人们的重视。
1970年美国专利(US3,697,516)是采用半胱氨酸盐与二硫化碳，在氢氧化钠存在下反应，制得(R)TTCA，产率仅有21.2％。1983年日本专利(KOKAIKOHO JP 38，276)是采用β-氯代丙氨酸与二硫化碳，在碱存在下环合制得(R)TTCA，产率为82％，但原料成本高。所以降低成本，提高产率成为人们所关注的课题。
本发明就是针对上述问题进行了研究，经过反复实验，取得实质性进展，从而完成了本发明。
本发明具有原料易得，成本低，合成方法简单，产率高等特点。
本发明是将L-半胱氨酸盐酸盐，二硫化碳，氢氧化钠及无机盐(Fe、Mn、Cr、Cd、Sn、Pb、Zn、Cu、Ba等金属的硫酸盐或硝酸盐或盐酸盐)溶于水中，在-15～85℃，其摩尔比为1∶0.8-1.1∶3-5∶0.8-1.1＝L-半胱氨酸盐酸盐∶CS2∶NaOH∶无机盐，搅拌反应1～2小时，滤出沉淀，用水洗沉淀，用盐酸中和滤液至中性，用乙酸乙酯萃取滤液，无水硫酸钠干燥萃取液，减压蒸出乙酸乙酯，得到略呈黄色的片状结晶(R)TTCA，产率85-92％。
实施例：取1.75g(10mmol)L-半胱氨酸盐酸盐，溶于含1.60g(mmol)氢氧化钠的30ml水中，加入0.65ml(10.7mmol)二硫化碳，搅拌到CS2全溶，加入1.53g硫酸亚铁及0.40g(10mmol)氢氧化钠，搅拌反应2小时，滤出沉淀，少许水洗两次，浓盐酸中和反应液，乙酸乙酯萃取，无水硫酸钠干燥，减压蒸出乙酸乙酯，得略呈黄色的片状晶体1.5g，产率91.8％；熔点180～181℃(盐酸重结晶)；[α]D 20-86°(C 1.039，0.5NHCL)。

Claims (2)

1.一种R-四氢噻唑-2-硫酮-4-羧酸的合成方法，该方法是使L-半胱氨酸、二硫化碳和氢氧化钠在选自金属硫酸盐、硝酸盐和盐酸盐的无机盐存在下进行反应。
2.如权利1所述的合成方法，其特征在于：反应摩尔比为，L-半胱氨酸∶CS2∶NaOH∶无机盐＝1∶0.8-1.1∶3-5∶0.8-1.1。
CN95100935A 1995-02-22 1995-02-22 Ｒ－四氢噻唑－２－硫酮－４－羧酸的合成方法 Expired - Fee Related CN1049218C (zh)

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CN95100935A CN1049218C (zh) 1995-02-22 1995-02-22 Ｒ－四氢噻唑－２－硫酮－４－羧酸的合成方法

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CN95100935A CN1049218C (zh) 1995-02-22 1995-02-22 Ｒ－四氢噻唑－２－硫酮－４－羧酸的合成方法

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CN1125228A CN1125228A (zh) 1996-06-26
CN1049218C true CN1049218C (zh) 2000-02-09

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108129417A (zh) * 2017-12-22 2018-06-08 中山市小榄企业服务有限公司 一种r-四氢噻唑-2-硫酮-4-羧酸的合成方法
CN116789617B (zh) * 2023-05-19 2024-05-28 郑州大学 一种高效黄色发光的手性Au2Cu2团簇材料及其在OLED中的应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960881A (en) * 1972-04-24 1976-06-01 Phillips Petroleum Company Method for preparing 4-carboxythiazolidine-2-thione
JPS5788171A (en) * 1980-11-19 1982-06-01 Mitsui Toatsu Chem Inc Synthetic method of compound containing sulfur
JPS5838276A (ja) * 1981-08-31 1983-03-05 Mitsui Toatsu Chem Inc ２−メルカプトチアゾリン−４−カルボン酸の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960881A (en) * 1972-04-24 1976-06-01 Phillips Petroleum Company Method for preparing 4-carboxythiazolidine-2-thione
JPS5788171A (en) * 1980-11-19 1982-06-01 Mitsui Toatsu Chem Inc Synthetic method of compound containing sulfur
JPS5838276A (ja) * 1981-08-31 1983-03-05 Mitsui Toatsu Chem Inc ２−メルカプトチアゾリン−４−カルボン酸の製造方法

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